Mixtures of new isomeric dyestuffs and process of preparing them



Patented Aug. 8,1933

UNITED} STATES PArfE' Tomes .MIXTURES of NEW ISOMERICV nYEsTUFrs AND PaocEss 0F PREPARING THEM Geerg Kr'sln'zlein, Heinrich Greunc, Martin Corell, and Heinrich Vollmann, Frankfort on the Main-Hochst, Germany, assignors to General Aniline Works, Inc., New York, N. 'Y.,- a Corporation of Delaware No Drawing. Application July 23;;1931, Serial No. 552,790, andjin Great Britain March 23',

14 Claims. (Cl. 260-44) 7 In the preceding-formula R stands iora sub-.

Our present invention relatesto mixtures of new isomeric dyestuffs and to processes of pre paring them. I v

This application contains subject matter in common with ourapplication Serial No. 342,662 filed February 25, 1929. g y

We have .iound that the condensation products of an aromatic ortho-diamine compound with. a benzenthrone-peri-dicarboxylic anhydride of the followinggeneral formula:

II a v O t=o 1 II V wherein the nuclei may contain substituents and a further benzene nucleus may be condensed in 5.6 or 7.8-position are valuable vat dyestufi r mixtures of good fastness properties.

Chemically these condensation products are imidazol derivatives which are formed from the anhydride of a benzanthrone peri-dicarboxylic acid and an ortho-diarnine by elimination of water: The condensation may be effected by heating the components either per se or in the presence of a diluent to a temperature exceeding 80 C. up to the boilingormelting temperature of the reaction mixture. The reaction, for instance, takes the following course:

I dyestuffs of the probable formulae:

1 1 1 o v N i l G c 7 C stituted or unsubstituted aromatic radical in which the two amino groups are in ortho-position to one another. v. p I According tothe present invention the condensation products are obtained-in the form of mixtures of isomeric dyestuffs-as shown by the above equation. a

As 'diluents there may be usedi nitrobenzene;

quinoline, glacial acetic acid, or the like; as orthodiamine there may be used; ortho-phenylene diamine and its nuclear substitution products, naphthalene-diamine, diamino-acenaphthene or the like. The free bases as well as their free salts may be used, but it is advantageousin the v latter case to addto the reaction mixture an'acid binding agent such assodium acetate or the like.

According to the present invention there are obtained as new products mixtures of isomeric wherein the nuclei may contain substituents and a further benzene nucleus 'may be condensed in 5.6- or 7.8position, the benzanthrone complexes in'the molecules of the isomeric dyestuffs, however, being identical and wherein R represents an aromatic radicle which may contain substituents and which is bound in two ortho-posi- 'tions to the nitrogen atoms V -The products as such have an intense coloration and as vatdyestuffs they are extremely qualified for dyeing and printing purposes.

;The following examples illustrate the invention, but they are not intended to' limit it there- 7 to, the parts being by weight: a

(1) 30 parts of benzanthroneperi-dicarboxylic anhydridei are intimately mixed with 16 parts of ortho-phenylene dianiine and the -mi-xture is heatedfor a short timeto about 180" C. to 200 v r C. ,whilestirring.- After cooling the mass'is'pul verized and extracted by means of hot diluted hydrochloric acid. The residue is an orange product which dissolves in sulfuric acid to a violet-red solution and dyes cotton from an alkaline hydrosulfite vat after exposure to the air orange tints of good properties as to fastness. The reaction probably proceeds in accordance with the following equation:

(2) 30 parts of benzanthrone-peri-dicarboxylic anhydride are mixed with 200 parts of nitrobenzene and 21.5 parts of para-chloro-orthophenylene diamine and the mixture is heated to boiling for about 30 minutes. After cooling, the

dyestufi which has been precipitated is filtered (3) 31.8 parts of benzanthrone-peri-dicarboxylic acid are heated to boiling with 200 parts of quinoline, 1'7 parts of para-ethoxy-orthophenylene diamine are then added thereto and the whole is further heated for about 20 minutes. After cooling, the dyestufi" which has been precipitated is filtered with suction and washed first with diluted hydrochloric acid and then with water. It is a brown product which dissolves in cold sulfuric acid toa violet solution and dyes cotton from an orange-red alkaline hydrosulfite vat deep brown tints.

(4) 30 parts of benzanthrone-peri-dicarboxylic anhydride are mixed with 290 parts of quinoline and 53 parts of LZ-naphthylene diamine sulfate.

1 The whole is heated to boiling for about 30 minutes. After cooling, the dyestuff which has been precipitated, is filteredwith suction and washed first with hot diluted hydrochloric acid and then with hot water. not which dissolves in concentrated sulfuric acid and The residue is a brown prodto a pure blue solution and dyes cotton from the red alkaline hydrosulfite vat beautiful deepbrown tints.

(5) 33.5 parts of '7-chl0ro-benzanthrone-peridicarboxylic anhydride are mixed with 200 parts of nitrobenzene and 13 parts of ortho-phenylene diamine. The whole is heated to boiling for a short time. The dyestuff thus obtained is filtered with suction after cooling and washed with alcohol. It is an orange colored powder which dyes cotton even tints.

(6) A mixture of 15 parts of benzanthroneperi-dicarboxylic anhydride, 7 parts of 2.3-diamino toluene and 300 parts of glacial acetic acid is heated to boiling and boiling is continued for several hours. The dyestufi? is then filtered with suction, while hot, and washed with hot alcohol. The residue is boiled twice with diluted caustic soda solution and washed until neutral. The dyestuff thus obtained dyes cotton from the vat brilliant scarlet tints. l

(7) A mixture of 15 parts of benzanthroneperi-dicarboxylic anhydricle, 12 parts of the hydrochloride of 2.3-diarnino-5-chloro-toluene, 300 parts of glacial acetic acid and 10 parts of fused sodium acetate is heated to boiling for several hours. The reaction mixture which first has a yellow color gradually assumes a red-brown coloration. The working up is the same as that described in Example 6. The shade of the dyestuff is as clear as that obtainable according to Example 6, only a little more yellow.

(8) A mixture of 15 parts of benzanthroneperi-dicarboxylic anhydride, 8 parts of 2-chloro- 4.5-diamino-toluene, 300 parts of glacial acetic acid and'2'parts of sodium acetate is heated to boiling for several hours on the reflux apparatus. The product is worked up in the usual manner. Thus a dye'stuff is obtained which dyes cotton a clear and brilliant orange tint.

(9) A mixture of 15 parts of benzanthroneperi-dicarboxylic anhydride, 9 parts of 2chloro' 4.5-diamino-anisol, 300 parts of glacial acetic acid and 2 parts of sodium acetate is heated to boiling for some hours. The dyestufi whichis precipitated'dyes cotton a clear brown tint.

parts of benzanthrone-peri-dicatrboxylic anhydride, 9 parts of 4.5-diamino-veratrol, 300 parts of glacial acetic acid and 2 parts of sodium acetate are heated to boiling for several hours. The dyestuif thus obtained dyes cotton 2. blackish-brown tint.

(11) parts of 5.6-benz-benzanthrone-peridicarboxylic anhydride (obtainable, for instance, by melting -a-naphthoyl-naphthalic anhydride with aluminium chloride) 11 parts of orthophenylene-diamine and 350 parts of glacial acetic acid are heated to boiling for some time, filtered with suction and the solid matter is washed with hot alcohol. In order to remove any unattached dicarboxylic anhydride the mass is boiled once With diluted caustic soda solution. The dyestuif thus obtained dissolves in concentrated sulfuric acid to a red solution and dyes cotton bluish-red tints.

(12 17.5 parts of '7.8-benz-benzanthrone-peridicarboxylic anhydride (obtainable, for instance,

I crystals. It dyes cotton from an alkaline hydrosulfite vat bluish-red tints of very good iastness properties.

(13) parts of monobromo-benzanthroneperi-dicarboxylic anhydride (obtainable by bromination of benzanthrone-peri-dicarboxylic anhydride) are treated with 400 parts of glacial acetic acid in the ballmill so as to become very finely subdivided; to this suspension are added 25 parts poi ortho-phenylene-diamine and the whole is finally heated on the reflux apparatus for half an hour, While stirring. The dyestuf'i which is left as residue on the filter after filtration and washing dissolves in concentrated sulfuric acid to a red-violet solution and dyes'cotton from the vat red-orange tints. I

We claim:

1. As new products, the mixtures of isomeric dyestufis of the probable formulae:

wherein the nuclei may contain halogen as sub- ,stituent, and a further benzene nucleus may be condensed in 5.6- or Lil-position, the benzanthrone complexes in the molecules of the isomeric i dyestuffs, however, being identical and wherein R represents an aromaticradical of the benzene and naphthalene series which is bound in two orthow Products, the mixtures: of isomeric dyestuffs of the probable formulae; V

wherein the nuclei may contain halogen as substituent and a further benzene nucleus may be condensed in. 5.6- or LS-position, the benzanthrone complexes in the molecules of the isomeric dyestufis, however, being identical, said products being vatdyestuffs of good fastness properties, having an intense coloration. p

, 3. As new products, the mixtures of isomeric wherein a further benzene nucleus may be condensed in 5.6- or 7.8-position, the benzanthrone complexes in the molecules of the isomeric dyestuffs, however, being identical and wherein X represents hydrogen or chlorine, said products being vat dyestuffs of good fastness-properties, having an intense coloration.

4. As new productsthe mixtures of isomeric dyestuffs of the formulae:

being orange products, dissolving in sulfuric acid to-a violet-red solution and dyeing cotton from an alkaline hydrosulfite'vat after exposure to the air orange tints of good 'fastness properties. w

5. As new products, the mixtures of isomeric dyestuffs of the probable formulae:

o 7 said products being orange, crystalline: powders, dissolving in concentrated sulfuric acid to a violet-red solution and dyeing cotton from a red alkaline hydrosulfite vat after exposure to the air clear orange tints.

6. As new products, the

dyestuffs of the formulae:

mixture of isomeric A ni said products being red crystals, dyeing cotton from an alkaline hydrosulfite vat bluish-red tints of very good fastness properties.

7. The process which comprises condensing an aromatic ortho-diamine with a benzanthroneperi-dicarboxylic anhydride of the following general formula:

wherein the nuclei may contain halogen as substituent and a further benzene nucleus may be condensed in 5.6- or lit-position, by heating to a temperature exceeding 30 C. up to the boiling or melting temperature of the reaction mixture.

9. The process which comprises condensing an aromatic ortho-diamine of the benzene series with a benzanthrone-peri-dicarboxylic anhydride of the following general formula wherein a further benzene nucleus may be condensed in 5.6- or YB-position, by heating to a temperature exceeding 80 C. up to the boiling or melting temperature of the reaction mixture.

11. The process which comprises condensing ortho-phenylene diamine with benzanthroneperi-dicarboxylic anhydride by heating the components for a short time to about 180 C. to 200 C. while stirring.

12. The process which comprises condensing para-chloro-ortho-phenylene diamine with benzanthrone-peri-dicarboxylic anhydride in the presence of nitrobenzene by heating the mixture to boiling for about 30 minutes. i

13. The process which comprises condensing the acetate of ortho-phenylene diamine with 7.8-benzo-benzanthrone-peri-dicarboxylic anhydride in the presence of nitrobenzene by heating the mixture to boiling for some time. 115

14. As new products, the mixtures of isomeric dyestuffs which are obtainable by the process which comprises condensing an aromatic orthodiamine with a benzanthrone-peri-dicarboxylic anhydride of the following general formula:

O r u /Y I C 8 1 go 7 2 GEORG KRANZLEIN. HEINRICH GREUNE. MARTIN CORELL. HEINRICH VOLLMANN. 

